EP2684849B1 - Method and device for treating drinking water - Google Patents
Method and device for treating drinking water Download PDFInfo
- Publication number
- EP2684849B1 EP2684849B1 EP13175555.5A EP13175555A EP2684849B1 EP 2684849 B1 EP2684849 B1 EP 2684849B1 EP 13175555 A EP13175555 A EP 13175555A EP 2684849 B1 EP2684849 B1 EP 2684849B1
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- European Patent Office
- Prior art keywords
- water
- corrosion inhibitor
- ion exchanger
- ions
- processed
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- 239000003651 drinking water Substances 0.000 title claims description 25
- 235000020188 drinking water Nutrition 0.000 title claims description 25
- 238000000034 method Methods 0.000 title claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 51
- 150000002500 ions Chemical class 0.000 claims description 45
- 230000007797 corrosion Effects 0.000 claims description 35
- 238000005260 corrosion Methods 0.000 claims description 35
- 239000003112 inhibitor Substances 0.000 claims description 27
- -1 hydrogen ions Chemical class 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 239000001257 hydrogen Substances 0.000 claims description 19
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 claims description 16
- 229910000400 magnesium phosphate tribasic Inorganic materials 0.000 claims description 16
- 230000036961 partial effect Effects 0.000 claims description 13
- 239000004135 Bone phosphate Substances 0.000 claims description 11
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 11
- 230000002378 acidificating effect Effects 0.000 claims description 10
- 150000001768 cations Chemical class 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims description 6
- 239000008187 granular material Substances 0.000 claims description 6
- 238000009434 installation Methods 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011343 solid material Substances 0.000 claims 2
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims 1
- 229910019142 PO4 Inorganic materials 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 6
- 235000021317 phosphate Nutrition 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229920000388 Polyphosphate Polymers 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 239000001205 polyphosphate Substances 0.000 description 3
- 235000011176 polyphosphates Nutrition 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000002308 calcification Effects 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010411 cooking Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229920001429 chelating resin Polymers 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 230000006735 deficit Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000002509 fulvic acid Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 235000012171 hot beverage Nutrition 0.000 description 1
- 239000004021 humic acid Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/18—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using inorganic inhibitors
- C23F11/184—Phosphorous, arsenic, antimony or bismuth containing compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/08—Corrosion inhibition
Definitions
- the invention relates to a method and a device for the treatment of drinking water in particular for water-bearing installations or devices, wherein water to be treated is at least partially softened by means of an ion exchanger by exchanging alkaline earth ions for hydrogen ions.
- the ion exchanger may also be only partially (for example 10-90%) in hydrogen form and otherwise in alkaline form, by the way.
- Water softening with resins and corrosion protection by phosphates are techniques from eg JP 2002 250794 and GB 299 074 known.
- a water filter is intended primarily to protect the devices from calcification and to remove any unwanted substances present in the drinking water.
- Undesirable impurities are, for example, organic substances such as humic and fulvic acids, residues of pesticides, chlorine and chlorine compounds, and heavy metals, which are usually dissolved out of pipelines and fittings.
- the removal of heavy metals is usually carried out by means of an ion exchanger.
- the ion exchanger has the task to protect the devices from calcification and to achieve a reduction in the carbonate hardness, especially in coffee machines and vending machines, to achieve a better taste.
- it is advantageous for the preparation of coffee when the carbonate hardness is about 6 - 8 ° d.
- an ion exchanger can be used, which is in the initial state predominantly in the hydrogen form.
- Such ion exchangers are cation exchangers which contain either sulfonic acid groups or carboxyl groups. The former are referred to as strongly acidic cation exchangers and the latter as weakly acidic cation exchangers.
- Commercially available strong acid cation exchangers are, for example, DOWEX HCR-S, AMBERLITE TM PWC14 and weakly acidic cation exchangers are, for example, Lewatit s 8227.
- An ion exchanger in the hydrogen form exchanges the cations of the drinking water for hydrogen ions of the ion exchanger according to the following scheme: Ca 2+ (drinking water) + 2 H + (ion exchanger) ⁇ Ca 2+ (ion exchanger) + 2 H + (drinking water) (1)
- the salt load in the water can be significantly reduced. Due to the formed carbonic acid, however, the treated drinking water becomes acidic, i. the pH is in a range of 4.3 to 6.8 well below the pH of the raw water. Although the pH shift effectively prevents the precipitation of calcium carbonate, the water after treatment is lime-aggressive and can cause corrosion in downstream equipment.
- the present invention seeks to further improve the known in the prior art treatment method and water filter and optimally adjusted by means of an ion exchanger water adjusted while maintaining the limescale due to the pH shift on, so that harmful effects on installations and Devices should be avoided if possible.
- the invention is based on the idea of using a corrosion inhibitor in combination with the ion exchanger in such a way that the hydrogen ions released into the water are buffered or neutralized, so that quality impairment of the drinking water is largely avoided and effective corrosion protection is achieved.
- the water to be treated is treated with a corrosion inhibitor formed by tricalcium diphosphate and / or trimagnesium diphosphate, wherein orthophosphate ions are added to the water.
- tertiary alkaline earth metal orthophosphates are difficult to dissolve in neutral water, they can, in combination with hydrogen ions, provide for an advantageous metering in of orthophosphate ions.
- a solution of hydrogen phosphate and dihydrogen phosphate forms with the hydrogen ions introduced from the ion exchanger; For example, at a pH of 6.6 about 40% is present as hydrogen phosphate and 60% as dihydrogen phosphate.
- the pH drops to a minimum value of 4.3.
- the orthophosphate ions on metallic surfaces promote the formation of protective oxide layers, which prevent further corrosion. It can also be achieved by adding orthophosphate, a reduction in the Entzinkungsne concerns copper-zinc alloys.
- Polycarbonate has also been proposed as a hardness stabilizer.
- corrosion protection can not be achieved by means of polyphosphate.
- the addition of polyphosphates actually increases the likelihood of corrosion by promoting the uniform removal of surface areas by polyphosphates, thus increasing copper solubility, for example.
- trimagnesium diphosphate In order to set a desired water quality, it is advantageous if a mixture of or with tricalcium diphosphate and trimagnesium diphosphate is used as a corrosion inhibitor, and if the proportion of trimagnesium diphosphate is less than 20% by mass.
- the corrosion inhibitor is brought as a solid, in particular as granules in contact with the water to be treated.
- the ion exchanger is advantageous for the ion exchanger to be provided as a weakly acidic or strongly acidic cation exchanger which is at least partially charged with hydrogen. It is also conceivable that the ion exchanger is in the range of 10 to 90% of its capacity (defined as the number of ion exchange groups per unit weight of the column packing material) in the hydrogen form and, for the remainder, optionally in the alkali form.
- an advantageous embodiment provides that the ion exchanger and the corrosion inhibitor are flowed through in a container by the water to be treated.
- At least a partial stream of the water to be treated is passed first over the ion exchanger and then over the corrosion inhibitor. It is conceivable, depending on the application, a reverse serial flow, so first on the corrosion inhibitor and then on the ion exchanger to keep the phosphate addition low.
- the water to be treated is filtered by means of an activated carbon filter.
- the corrosion inhibitor contains tricalcium diphosphate, trimagnesium diphosphate or a mixture thereof or, wherein in a mixture, the proportion of trimagnesium diphosphate is less than 20% by mass.
- the ion exchanger and the corrosion inhibitor are arranged in a container provided with a water inlet and a water outlet.
- a further simplification results from the fact that the container in the form of a consumable in a water-carrying device disposable cartridge is formed, and that the corrosion inhibitor is flowed through as a solid bed of the water to be treated.
- the devices shown in the drawing consist essentially of a water treatment cartridge 1, which contains an ion exchange material 2, a granular bed 3 of tricalcium diphosphate Ca 3 (PO 4 ) 2 and / or trimagnesium diphosphate Mg 3 (PO 4 ) 2 and an activated carbon filter 11.
- a water treatment cartridge 1 which contains an ion exchange material 2
- the granules in the granulated bed 3 have a particle diameter of 0.2 to 5 mm.
- the drinking water to be treated is passed via an inlet 4 into the water treatment cartridge 1 and first flows through the granulate bed 3 and then the ion exchanger 2, which is predominantly in the hydrogen form. Then, the water flows through the activated carbon filter 11. The treated water can be removed via the drain 5 from the water treatment cartridge 1.
- a small amount of the tertiary ortho-phosphates dissolves.
- a mixture of tricalcium diphosphate and trimagnesium diphosphate wherein the proportion of trimagnesium diphosphate is less than 20% by mass, and preferably about 15% by mass, optimal concentrations are achieved in the drinking water.
- the phosphate concentration below the maximum values required by the Drinking Water Ordinance is approx. 2 ppm.
- the hardness formers of the drinking water are replaced by the hydrogen ions of the ion exchange material.
- the phosphate ions dissolved in the water react with the hydrogen ions.
- hydrogen phosphate ions or dihydrogen phosphate ions are formed in accordance with the above equation (3) and (4).
- the pH is buffered and at the same time corrosion inhibitors are formed.
- the drinking water is first passed through an ion exchanger 2 located predominantly in the hydrogen form, wherein the hardness formers of the drinking water are replaced by the hydrogen ions of the exchanger and the pH value of the drinking water is lowered. Subsequently, the total flow of acidic drinking water is passed through a bed consisting of granules of tricalcium diphosphate and / or trimagnesium diphosphate. Due to the lower pH, the solubility of the orthophosphate increases, and the dissolved content is correspondingly high (> 100 ppm).
- Fig. 3 to 6 show different embodiments of the division of part streams in the cartridge 1. In this case, depending on the ratio between ion exchange and Granualtstrom the amount of dissolved phosphate can be adjusted.
- Fig. 3 The entire drinking water to be treated first flows through the granulate bed 3.
- a partial stream 7 is passed through the ion exchanger 2, while the other partial stream 6 flows directly to the activated carbon bed 11.
- the partial streams 6 and 7 are passed together through the activated carbon filter 11.
- Fig. 5 shows a variant in which a partial stream 8 is passed over the ion exchanger 2. Subsequently, the treated via the ion exchanger water 7 is passed directly into the granulated bed 3. Before the activated carbon filter 11 is a waste with the untreated partial stream. 9
- a partial stream 8 is passed over the ion exchanger 2, while a further partial stream 10 is guided past it in parallel.
- the two partial streams 7 and 10 are passed together over the granulated bed 3.
- the total flow is passed through an activated carbon bed 11 to the outlet 5 and leaves the water treatment cartridge.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Treatment Of Water By Ion Exchange (AREA)
- Water Treatment By Sorption (AREA)
Description
Die Erfindung betrifft ein Verfahren und eine Vorrichtung zur Aufbereitung von Trinkwasser insbesondere für wasserführende Installationen oder Geräte, wobei aufzubereitendes Wasser mittels eines Ionenaustauschers durch Austausch von Erdalkali-Ionen gegen Wasserstoff-Ionen zumindest teilweise enthärtet wird. Der Ionenaustauscher kann sich dabei auch nur zu einem Teil (z.B. 10-90%) in Wasserstoffform und im Übrigen beispielsweise in Alkaliform befinden.The invention relates to a method and a device for the treatment of drinking water in particular for water-bearing installations or devices, wherein water to be treated is at least partially softened by means of an ion exchanger by exchanging alkaline earth ions for hydrogen ions. The ion exchanger may also be only partially (for example 10-90%) in hydrogen form and otherwise in alkaline form, by the way.
Wasserenthärtung mit Harzen und Korrosionsschutz durch Phosphate sind Techniken aus z.B.
Die Entfernung von Schwermetallen wird in der Regel mittels eines Ionenaustauschers durchgeführt. Weiterhin hat der Ionenaustauscher die Aufgabe, die Geräte vor Verkalkung zu schützen und insbesondere bei Kaffeemaschinen und Getränkeautomaten auch zur Erzielung eines besseren Geschmacks eine Reduktion der Karbonathärte zu erreichen. Beispielsweise ist es für die Zubereitung von Kaffee vorteilhaft, wenn die Karbonathärte bei ca. 6 - 8 °d liegt. Zur Reduktion der Karbonathärte kann ein Ionenaustauscher eingesetzt werden, welcher sich im Ausgangszustand überwiegend in der Wasserstoffform befindet. Solche Ionenaustauscher sind Kationenaustauscher, welche entweder Sulfonsäuregruppen oder aber Carboxylgruppen enthalten. Erstere werden als stark saure Kationenaustauscher und letztere als schwach saure Kationenaustauscher bezeichnet. Handelsübliche stark saure Kationenaustauscher sind zum Beispiel DOWEX HCR-S, AMBERLITE™ PWC14 und schwach saure Kationenaustauscher sind zum Beispiel Lewatit s 8227.The removal of heavy metals is usually carried out by means of an ion exchanger. Furthermore, the ion exchanger has the task to protect the devices from calcification and to achieve a reduction in the carbonate hardness, especially in coffee machines and vending machines, to achieve a better taste. For example, it is advantageous for the preparation of coffee when the carbonate hardness is about 6 - 8 ° d. To reduce the carbonate hardness, an ion exchanger can be used, which is in the initial state predominantly in the hydrogen form. Such ion exchangers are cation exchangers which contain either sulfonic acid groups or carboxyl groups. The former are referred to as strongly acidic cation exchangers and the latter as weakly acidic cation exchangers. Commercially available strong acid cation exchangers are, for example, DOWEX HCR-S, AMBERLITE ™ PWC14 and weakly acidic cation exchangers are, for example, Lewatit s 8227.
Ein Ionenaustauscher in der Wasserstoffform tauscht nach folgendem Schema die Kationen des Trinkwassers gegen Wasserstoffionen des Ionenaustauschers aus:
Ca2+ (Trinkwasser) + 2 H+ (Ionenaustauscher) → Ca2+ (Ionenaustauscher) + 2 H+ (Trinkwasser) (1)
An ion exchanger in the hydrogen form exchanges the cations of the drinking water for hydrogen ions of the ion exchanger according to the following scheme:
Ca 2+ (drinking water) + 2 H + (ion exchanger) → Ca 2+ (ion exchanger) + 2 H + (drinking water) (1)
Die Wasserstoffionen aus dem Ionenaustauscher reagieren mit den Hydrogencarbonationen des Trinkwassers nach folgendem Schema:
2 H+ + 2 HCO3 - → H2CO3 (2)
The hydrogen ions from the ion exchanger react with the bicarbonate ions of the drinking water according to the following scheme:
2 H + + 2 HCO 3 - → H 2 CO 3 (2)
Es entsteht somit Kohlensäure. Durch die Entfernung der Härtebildner, als auch die Bildung der Kohlensäure, kann die Salzfracht im Wasser deutlich verringert werden. Aufgrund der gebildeten Kohlensäure wird das aufbereitete Trinkwasser allerdings sauer, d.h. der pH-Wert liegt in einem Bereich von 4,3 bis 6,8 deutlich unter dem pH-Wert des Rohwassers. Zwar verhindert die pH-Verschiebung effektiv die Ausfällung von Calciumcarbonat, jedoch ist das Wasser nach der Aufbereitung kalkaggressiv und kann dadurch Korrosion in den nachfolgenden Geräten auslösen.It thus produces carbon dioxide. By removing the hardness formers, as well as the formation of carbonic acid, the salt load in the water can be significantly reduced. Due to the formed carbonic acid, however, the treated drinking water becomes acidic, i. the pH is in a range of 4.3 to 6.8 well below the pH of the raw water. Although the pH shift effectively prevents the precipitation of calcium carbonate, the water after treatment is lime-aggressive and can cause corrosion in downstream equipment.
Ausgehend hiervon liegt der Erfindung die Aufgabe zugrunde, die im Stand der Technik bekannten Aufbereitungsverfahren und Wasserfilter weiter zu verbessern und ein mittels eines Ionenaustauschers sauer eingestelltes Wasser möglichst unter Aufrechterhaltung des Kalkschutzes infolge der pH-Verschiebung weiter zu optimieren, so dass schädliche Auswirkungen auf Installationen und Geräte möglichst vermieden werden.Proceeding from this, the present invention seeks to further improve the known in the prior art treatment method and water filter and optimally adjusted by means of an ion exchanger water adjusted while maintaining the limescale due to the pH shift on, so that harmful effects on installations and Devices should be avoided if possible.
Zur Lösung dieser Aufgabe wird die im Patentanspruch 1 bzw. 9 angegebene Merkmalskombination vorgeschlagen. Vorteilhafte Ausgestaltungen und Weiterbildungen der Erfindung ergeben sich aus den abhängigen Ansprüchen. Die Erfindung geht von dem Gedanken aus, einen Korrosionshemmstoff in Kombination mit dem Ionenaustauscher so einzusetzen, dass die in das Wasser abgegebenen Wasserstoffionen abgepuffert bzw. neutralisiert werden, so dass eine Qualitätsbeeinträchtigung des Trinkwassers weitgehend vermieden und ein effektiver Korrosionsschutz erzielt wird.To solve this problem, the combination of features specified in
Demzufolge wird in verfahrensmäßiger Hinsicht vorgeschlagen, dass das aufzubereitende Wasser mit einem durch Tricalciumdiphosphat und/oder Trimagnesiumdiphosphat gebildeten Korrosionsinhibitor behandelt wird, wobei dem Wasser Orthophosphat-Ionen zugesetzt werden.Accordingly, it is proposed in the procedural aspect that the water to be treated is treated with a corrosion inhibitor formed by tricalcium diphosphate and / or trimagnesium diphosphate, wherein orthophosphate ions are added to the water.
Tertiäre Erdalkali-Orthophosphate sind zwar für sich in neutralem Wasser nur schwer löslich, können aber in Verbindung mit Wasserstoffionen für eine vorteilhafte Eindosierung von Orthophosphat-Ionen sorgen. Hierbei bildet sich je nach pH-Wert des Wassers mit den aus dem Ionenaustauscher eingebrachten Wasserstoffionen eine Lösung aus Hydrogenphosphat und Dihydrogenphosphat; so liegt zum Beispiel bei einem pH-Wert von 6,6 ca. ca. 40% als Hydrogenphosphat und 60% als Dihydrogenphosphat vor. Die aggressiven Wasserstoffionen werden dabei nach folgender Reaktion abgepuffert bzw. neutralisiert:
(PO4 3-) + H+ ↔ (HPO4 2-) pKa = 12.1 (3)
(HPO4 2-) + H+ ↔ (H2PO4 -) pKa = 7.2 (4)
Although tertiary alkaline earth metal orthophosphates are difficult to dissolve in neutral water, they can, in combination with hydrogen ions, provide for an advantageous metering in of orthophosphate ions. Depending on the pH of the water, a solution of hydrogen phosphate and dihydrogen phosphate forms with the hydrogen ions introduced from the ion exchanger; For example, at a pH of 6.6 about 40% is present as hydrogen phosphate and 60% as dihydrogen phosphate. The aggressive hydrogen ions become weaker buffered or neutralized the following reaction:
(PO 4 3- ) + H + ↔ (HPO 4 2- ) pKa = 12.1 (3)
(HPO 4 2- ) + H + ↔ (H 2 PO 4 - ) pKa = 7.2 (4)
Bei Einsatz eines schwach sauren Ionenaustauschers, bei welchem nur die an die Karbonathärte gebundenen Calcium- bzw. Magnesiumionen des Wassers gegen die Wasserstoffionen des Ionenaustauschers ausgetauscht werden, sinkt der pH-Wert auf einen minimalen Wert von 4,3. Üblicherweise liegen die pH-Werte des Trinkwassers nach dem Ionenaustauscher und nach einer nach den Gl. (3) und (4) erfolgten Reaktion in einem pH-Bereich zwischen 6.0 und 7.0.When using a weakly acidic ion exchanger, in which only the bound to the carbonate hardness calcium or magnesium ions of the water are exchanged for the hydrogen ions of the ion exchanger, the pH drops to a minimum value of 4.3. Usually, the pH values of the drinking water after the ion exchanger and according to the Eq. (3) and (4) reaction in a pH range between 6.0 and 7.0.
Die Orthophosphat-Ionen begünstigen auf metallischen Oberflächen die Ausbildung von schützenden Oxidschichten, welche die weitere Korrosion verhindern. Ebenfalls kann durch Zugabe von Orthophosphat eine Verringerung der Entzinkungsneigung von Kupfer-Zinklegierungen erreicht werden.The orthophosphate ions on metallic surfaces promote the formation of protective oxide layers, which prevent further corrosion. It can also be achieved by adding orthophosphate, a reduction in the Entzinkungsneigung copper-zinc alloys.
Im Unterschied zu herkömmlichen Korrosionsschutzmaßnahmen, die auf dem Einsatz von Alkali- (Natrium, Kalium)-phosphaten beruhen, lassen sich mit den erfindungsgemäßen Maßnahmen geringe Substanzmengen hinreichend genau eindosieren. Hingegen arbeiten die bekannten Dosierschleusen für Alkali-Orthophosphate aufgrund von dessen guter Löslichkeit sehr ungenau und sind deshalb für den Einsatz im Trinkwasser eher nicht geeignet.In contrast to conventional corrosion protection measures, which are based on the use of alkali metal (sodium, potassium) phosphates, it is possible with the measures according to the invention to meter small amounts of substance with sufficient accuracy. On the other hand, the known metering locks for alkali orthophosphates work due to its good solubility are very inaccurate and therefore rather not suitable for use in drinking water.
Als Härtestabilisator wurde auch schon Polyphosphat vorgeschlagen. Ein Korrosionsschutz lässt sich jedoch mittels Polyphosphat nicht erzielen. Durch Zugabe von Polyphosphaten wird die Korrosionswahrscheinlichkeit sogar erhöht, indem Polyphosphate den gleichmäßigen Flächenabtrag fördern und so zum Beispiel die Kupferlöslichkeit erhöhen.Polycarbonate has also been proposed as a hardness stabilizer. However, corrosion protection can not be achieved by means of polyphosphate. The addition of polyphosphates actually increases the likelihood of corrosion by promoting the uniform removal of surface areas by polyphosphates, thus increasing copper solubility, for example.
Um eine gewünschte Wasserqualität einzustellen, ist es vorteilhaft, wenn eine Mischung aus bzw. mit Tricalciumdiphosphat und Trimagnesiumdiphosphat als Korrosionsinhibitor eingesetzt wird, und wenn dabei der Anteil von Trimagnesiumdiphosphat weniger als 20 Massen-% beträgt.In order to set a desired water quality, it is advantageous if a mixture of or with tricalcium diphosphate and trimagnesium diphosphate is used as a corrosion inhibitor, and if the proportion of trimagnesium diphosphate is less than 20% by mass.
Für eine vereinfachte Handhabung ist es günstig, wenn der Korrosionsinhibitor als Feststoff, insbesondere als Granulat in Kontakt mit dem aufzubereitenden Wasser gebracht wird.For a simplified handling, it is advantageous if the corrosion inhibitor is brought as a solid, in particular as granules in contact with the water to be treated.
Für eine synergistische Wirkung in Verbindung mit dem Korrosionsinhibitor ist es vorteilhaft, wenn der Ionenaustauscher als mit Wasserstoff zumindest teilweise beladener, schwach saurer oder stark saurer Kationenaustauscher bereitgestellt wird. Denkbar ist es auch, dass sich der Ionenaustauscher im Bereich von 10 bis 90% seiner Kapazität (definiert als Zahl der Ionenaustauschergruppen pro Gewichtseinheit des Säulenfüllmaterials) in der Wasserstoffform und für den Rest ggf. in der Alkaliform befindet.For a synergistic effect in conjunction with the corrosion inhibitor, it is advantageous for the ion exchanger to be provided as a weakly acidic or strongly acidic cation exchanger which is at least partially charged with hydrogen. It is also conceivable that the ion exchanger is in the range of 10 to 90% of its capacity (defined as the number of ion exchange groups per unit weight of the column packing material) in the hydrogen form and, for the remainder, optionally in the alkali form.
Sowohl zur Korrosionshemmung als auch zur Qualitätsverbesserung beispielsweise im Hinblick auf die Zubereitung von Heißgetränken ist es vorteilhaft, wenn der ph-Wert des aus dem Ionenaustauscher mit Wasserstoff-Ionen beladenen Wassers durch den Korrosionsinhibitor unter Bildung von Hydrogenphosphat-Ionen bzw. Dihydrogenphosphat-Ionen erhöht und/oder abgepuffert wird.Both for inhibiting corrosion and for improving the quality, for example, with regard to the preparation of hot drinks, it is advantageous if the pH value of the loaded from the ion exchanger with hydrogen ions water increased by the corrosion inhibitor to form hydrogen phosphate ions or dihydrogen phosphate ions and / or buffered.
Um die Bereitstellung und Anwendung weiter zu vereinfachen, sieht eine vorteilhafte Ausführung vor, dass der Ionenaustauscher und der Korrosionsinhibitor in einem Behältnis von dem aufzubereitenden Wasser durchströmt werden.To further simplify the provision and application, an advantageous embodiment provides that the ion exchanger and the corrosion inhibitor are flowed through in a container by the water to be treated.
Um die Löslichkeit des Korrosionsinhibitors zu verbessern, ist es vorteilhaft, wenn zumindest ein Teilstrom des aufzubereitenden Wassers zuerst über den Ionenaustauscher und dann über den Korrosionsinhibitor geleitet wird. Denkbar ist je nach Anwendungsfall auch eine umgekehrte serielle Durchströmung, also zuerst über den Korrosionsinhibitor und dann über den Ionenaustauscher, um die Phosphat-Zudosierung gering zu halten.In order to improve the solubility of the corrosion inhibitor, it is advantageous if at least a partial stream of the water to be treated is passed first over the ion exchanger and then over the corrosion inhibitor. It is conceivable, depending on the application, a reverse serial flow, so first on the corrosion inhibitor and then on the ion exchanger to keep the phosphate addition low.
Zur Entfernung unerwünschter Substanzen ist es vorteilhaft, wenn das aufzubereitende Wasser mittels eines Aktivkohlefilters filtriert wird.To remove unwanted substances, it is advantageous if the water to be treated is filtered by means of an activated carbon filter.
Im Hinblick auf eine Vorrichtung zur Wasseraufbereitung von Trinkwasser insbesondere für wasserführende Installationen oder Geräte wird die eingangs genannte Aufgabe durch die Kombination eines zur Enthärtung des aufzubereitenden Wassers durch Austausch von Erdalkali-Ionen gegen Wasserstoff-Ionen eingerichteten Ionenaustauschers und eines durch Erdalkali-Orthophosphate in Form von Tricalciumdiphosphat und/oder Trimagnesiumdiphosphat gebildeten Korrosionsinhibitors gelöst.With regard to a device for water treatment of drinking water in particular for water-bearing installations or equipment, the object mentioned by the combination of a water softening of the water to be treated by exchange of alkaline earth ions against hydrogen ions ion exchangers and one by alkaline earth metal orthophosphates in the form of Tricalcium diphosphate and / or trimagnesium diphosphate formed corrosion inhibitor.
Vorteilhafterweise enthält der Korrosionsinhibitor Tricalciumdiphosphat, Trimagnesiumdiphosphat oder eine Mischung davon bzw. damit, wobei in einer Mischung der Anteil von Trimagnesiumdiphosphat weniger als 20 Massen-% beträgt.Advantageously, the corrosion inhibitor contains tricalcium diphosphate, trimagnesium diphosphate or a mixture thereof or, wherein in a mixture, the proportion of trimagnesium diphosphate is less than 20% by mass.
Für eine vereinfachte Handhabung ist es auch von Vorteil, wenn der Ionenaustauscher und der Korrosionsinhibitor in einem mit einem Wasserzulauf und einem Wasserablauf versehenen Behälter angeordnet sind.For a simplified handling, it is also advantageous if the ion exchanger and the corrosion inhibitor are arranged in a container provided with a water inlet and a water outlet.
Eine weitere Vereinfachung ergibt sich dadurch, dass der Behälter in Form einer als Verbrauchsmittel in ein wasserführendes Gerät einwechselbaren Kartusche ausgebildet ist, und dass der Korrosionsinhibitor als Feststoffschüttung von dem aufzubereitenden Wasser durchströmbar ist.A further simplification results from the fact that the container in the form of a consumable in a water-carrying device disposable cartridge is formed, and that the corrosion inhibitor is flowed through as a solid bed of the water to be treated.
Im Folgenden wird die Erfindung anhand der in der Zeichnung in schematischer Weise dargestellten Ausführungsbeispiele näher erläutert. Es zeigen
- Fig. 1
- eine Vorrichtung zur Wasserbehandlung umfassend einen Ionenaustauscher und einen Korrosionsinhibitor in einer schaubildlichen Darstellung;
- Fig. 2 - 6
- weitere Ausführungsbeispiele mit unterschiedlicher Anordnung von Ionenaustauscher und Korrosionsinhibitor in einer
Fig. 1 entsprechenden Darstellung.
- Fig. 1
- a device for water treatment comprising an ion exchanger and a corrosion inhibitor in a diagrammatic representation;
- Fig. 2-6
- Further embodiments with different arrangement of ion exchanger and corrosion inhibitor in one
Fig. 1 corresponding representation.
Die in der Zeichnung dargestellten Vorrichtungen bestehen im Wesentlichen aus einer Wasseraufbereitungskartusche 1, welche ein Ionenaustauschermaterial 2, eine Granulatschüttung 3 aus Tricalciumdiphosphat Ca3(PO4)2 und/oder Trimagnesiumdiphosphat Mg3(PO4)2 und ein Aktivkohlefilter 11 enthält. Zweckmäßig haben die Granulate in der Granulatschüttung 3 einen Korndurchmesser von 0,2 bis 5 mm.The devices shown in the drawing consist essentially of a
In der Anordnung nach
Bei der Durchströmung der Granulatschüttung 3 löst sich eine kleine Menge der tertiären ortho-Phosphate. Insbesondere bei Verwendung einer Mischung aus Tricalciumdiphosphat und Trimagnesiumdiphosphat, wobei der Anteil an Trimagnesiumdiphosphat bei weniger als 20 Massen% und vorzugsweise bei ca. 15 Massen% liegt, werden optimale Konzentrationen im Trinkwasser erreicht. In diesem Fall liegt die Phosphatkonzentration unterhalb der von der Trinkwasserverordnung geforderten Höchstwerte bei ca. 2 ppm.When flowing through the
In dem Ionenaustauscher werden die Härtebildner des Trinkwassers durch die Wasserstoffionen des Ionenaustauschermaterials ersetzt. Die in dem Wasser gelösten Phosphationen reagieren mit den Wasserstoffionen. Dabei bilden sich Hydrogenphosphat-Ionen bzw. Dihydrogenphosphat-Ionen gemäß vorstehender Gleichung (3) und (4). Der pH-Wert wird abgepuffert und gleichzeitig entstehen Korrosionshemmstoffe.In the ion exchanger, the hardness formers of the drinking water are replaced by the hydrogen ions of the ion exchange material. The phosphate ions dissolved in the water react with the hydrogen ions. In this case, hydrogen phosphate ions or dihydrogen phosphate ions are formed in accordance with the above equation (3) and (4). The pH is buffered and at the same time corrosion inhibitors are formed.
In einer weiteren Ausführung gemäß
Die weiteren
Gemäß
Nach
In der Alternative nach
Claims (11)
- Method for processing drinking water, in particular for water-carrying installations or apparatuses, in which method water to be processed is softened by means of an ion exchanger (2) by exchanging alkaline earth ions for hydrogen ions, characterized in that the water to be processed is treated with a corrosion inhibitor (3) formed by tricalcium diphosphate and/or trimagnesium diphosphate, the pH value of the water charged with hydrogen ions from the ion exchanger (2) being increased and/or buffered by the corrosion inhibitor (3) to form hydrogen phosphate ions or dihydrogen phosphate ions.
- Method according to claim 1, characterized in that a mixture consisting of tricalcium diphosphate and trimagnesium diphosphate is used as the corrosion inhibitor (3), the proportion of trimagnesium phosphate being less than 20% by mass.
- Method according to either claim 1 or claim 2, characterized in that the corrosion inhibitor (3) is brought into contact, as a solid material, in particular as granular material, with the water to be processed.
- Method according to any of claims 1 to 3, characterized in that the ion exchanger (2) is provided as a weakly acidic or strongly acidic cation exchanger that is at least partially charged with hydrogen.
- Method according to any of claims 1 to 4, characterized in that the water to be processed is conveyed in a container (1) via the ion exchanger (2) and the corrosion inhibitor (3).
- Method according to any of claims 1 to 5, characterized in that at least a partial stream of the water to be processed is first guided via the ion exchanger (2) and then via the corrosion inhibitor (3), or vice versa.
- Method according to any of claims 1 to 6, characterized in that the water to be processed is filtered by means of an activated carbon filter (11).
- Device for processing drinking water, in particular for water-carrying installations or apparatuses, comprising an ion exchanger (2) designed to soften the water to be processed by exchanging alkaline earth metal ions for hydrogen ions, and a corrosion inhibitor (3) formed by tricalcium diphosphate, trimagnesium diphosphate or a mixture thereof for introducing orthophosphate ions into the water to be processed, wherein the ion exchanger (2) and the corrosion inhibitor (3) are arranged in a container (1) that is provided with a water inlet (4) and a water outlet (5) and the pH value of the water charged with hydrogen ions from the ion exchanger (2) is increased and/or buffered by the corrosion inhibitor (3) to form hydrogen phosphate ions or dihydrogen phosphate ions.
- Device according to claim 8, characterized in that the proportion of trimagnesium phosphate in the mixture consisting of tricalcium diphosphate and trimagnesium diphosphate is less than 20% by mass.
- Device according to either claim 8 or claim 9, characterized in that the container (1) is in the form of a cartridge which can be replaced as a consumable in a water-carrying apparatus.
- Device according to any of claims 8 to 10, characterized in that the water to be processed can flow through the corrosion inhibitor (3) which is formed as a solid material filling.
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DE102012211903.5A DE102012211903A1 (en) | 2012-07-09 | 2012-07-09 | Process and device for the treatment of drinking water |
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DE (1) | DE102012211903A1 (en) |
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DE102014101285A1 (en) | 2014-02-03 | 2015-08-06 | Hans Sasserath Gmbh & Co. Kg | Arrangement for softening drinking water |
DE202015101168U1 (en) | 2015-03-09 | 2015-03-19 | Bwt Wassertechnik Gmbh | Water treatment device with metering device |
DE102015112778A1 (en) * | 2015-08-04 | 2017-02-09 | Bwt Ag | Apparatus and method for enriching water with minerals |
WO2019154768A1 (en) * | 2018-02-09 | 2019-08-15 | Aquis Wasser-Luft-Systeme Gmbh, Lindau, Zweigniederlassung Rebstein | Water hardness stabilization with anion exchanger |
DE102019132318A1 (en) * | 2019-11-28 | 2021-06-02 | Bwt Ag | Method and device for corrosion protection |
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JP3849925B2 (en) * | 2000-12-21 | 2006-11-22 | 株式会社東芝 | Chemical decontamination method |
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